Merocyanine Derivatives for Cosmetic Use

ABSTRACT

Described are merocyanine derivatives of formula (1a) or (1b) wherein n and o are integers from 2 to 4 and aminocyclohexenone intermediates. They are used in protecting human and animal hair and skin from UV radiation.

The present invention relates to the use of merocyanine derivatives inprotecting human and animal hair and skin from UV radiation and tocosmetic compositions comprising such compounds.

The compounds for use in accordance with the invention correspond toformula

wherein

-   R₂ is hydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted or    C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl; or a cyano group;-   R₄ is a cyano group; or -Q₁-R₅;-   Q₁ is —COO—; —CONH—; —CO—; —SO₂—; or —CONR₆—;-   R₅ is C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; or unsubstituted or    C₁-C₆alkyl-substituted C₆-C₂₀aryl;-   R₆ is hydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted or    C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl;-   the cyclohexene radical C is not substituted or substituted by one    or more C₁-C₅alkyl;-   n is from 2 to 4;-   o is from 2 to 4;-   if n=2, in formula (1a)-   R₁ is an alkylene, cycloalkylene or phenylene-radical; or R₁ and R₂    simultaneously form an alkylene, cycloalkylene or phenylene radical;    and-   R₃ is a cyano group; or -Q₁-R₅; or R₃ and R₄ together form a 5- to    7-membered, monocyclic carbocyclic ring, which is optionally    interrupted by —O— or —NR₇—;-   If o=2, in formula (1b)-   R₃ is an alkylene, cycloalkylene or phenylene radical, which is    optionally substituted with C₁-C₄alkyl, C₁-C₄alkoxy, —COR₆, —COOR₆    or —CONHR₆; and-   R₁ is hydrogen; a cyano group; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl;    unsubstituted or C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl;    or R₁ and R₂ together with the nitrogen atom linking them form a    —(CH₂)_(m)— ring which is optionally interrupted by —O— or by —NR₇—;-   R₇ is hydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted or    C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl;-   m is a number from 3 to 7;-   if n=3, in formula (1a)-   R₁ is a trivalent alkyl group, which is optionally interrupted by    one or more —O— or —NR₇-groups; and-   R₃ is a cyano group; or -Q₁-R₅; or R₃ and R₄ together form a 5- to    7-membered, monocyclic carbocyclic ring;-   if o=3, in formula (1b)-   R₃ is an alkylidene, cycloalkylidene or phenylidene radical; and-   R₁ is hydrogen; a cyano group; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl;    unsubstituted or C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl;    or R₁ and R₂ together with the nitrogen atom linking them form a    —(CH₂)_(m)— ring which is optionally interrupted by —O— or by —NR₇—;-   if n=4, in formula (1a)-   R₁ is a tetravalent alkyl group; and-   R₃ is a cyano group or -Q₁-R₅; or R₃ and R₄ together form a 5- to    7-membered, monocyclic carbocyclic ring;-   if o=4, in formula (1b)-   R₃ is a tetravalent alkyl group; and-   R₁ is hydrogen; a cyano group; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl;    unsubstituted or C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl;    or R₁ and R₂ together with the nitrogen atom linking them form a    —(CH₂)_(m)— ring which is optionally interrupted by —O— or by —NR₇—.

C₁-C₂₂Alkyl denotes a linear or branched, unsubstituted or substitutedalkyl group such as, for example, methyl, ethyl, propyl, isopropyl,n-butyl, n-hexyl, cyclohexyl, n-decyl, n-dodecyl, n-octadecyl, eicosyl,methoxyethyl, ethoxypropyl, 2-ethylhexyl, hydroxyethyl, chloropropyl,N,N-diethylaminopropyl, cyanoethyl, phenethyl, benzyl,p-tert-butylphenethyl, p-tert-octyl-phenoxyethyl,3-(2,4-di-tert-amylphenoxy)-propyl,ethoxycarbonylmethyl-2-(2-hydroxyethoxy)ethyl or 2-furylethyl.

C₁-C₆alkoxy denotes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy.

C₆-C₁₀aryl denotes, for example, phenyl, tolyl, anisyl, mesityl,chlorophenyl, 2,4-di-tert-amylphenyl and naphthyl.

Heterocyclic radicals contain one, two, three or four identical ordifferent ring hetero atoms. Special preference is given to heterocycleswhich contain one, two or three, especially one or two, identical ordifferent hetero atoms. The heterocycles may be mono- or poly-cyclic,for example mono-, bi- or tri-cyclic. They are preferably mono- orbi-cyclic, especially mono-cyclic. The rings preferably contain 5, 6 or7 ring members. Examples of monocyclic and bicyclic heterocyclic systemsfrom which radicals occurring in the compounds of formula (1a) and (1b)may be derived are, for example, pyrrole, furan, thiophene, imidazole,pyrazole, 1,2,3-triazole, 1,2,4-triazole, pyridine, pyridazine,pyrimidine, pyrazine, pyran, thiopyran, 1,4-dioxane, 1,2-oxazine,1,3-oxazine, 1,4-oxazine, indole, benzothiophene, benzofuran,pyrrolidine, piperidine, piperazine, morpholine and thiomorpholine.

When R₅ and R₆ together form a 5- to 7-membered monocyclic carbocyclicor heterocyclic ring, such a ring is, for example, a1,3-dioxocyclohexane ring such as, for example, a dime-done ring, a1,3-dioxo-5,5-diethylcyclohexane ring, a1,3-diaza-2,4,6-trioxocyclohexane ring such as, for example, abarbituric acid ring, a 1,3-dimethylbarbituric acid ring, a1-phenylbarbituric acid ring, a 1-methyl-3-octylbarbituric acid ring, a1-ethyl-3-octyloxycarbonylethylbarbituric acid ring, a1,2-diaza-3,5-dioxocyclopentane ring such as, for example, a1,2-diaza-1,2-dimethyl-3,5-dioxocyclopentane ring, a1,2-diaza-1,2-diphenyl-3,5-dioxocyclopentane ring, or a2,4-diaza-1-alkoxy-3,5-dioxocyclohexene ring such as, for example, a2,4-diaza-1-ethoxy-4-ethyl-3,5-dioxocyclohexene ring, a2,4-diaza-1-ethoxy-4-[3-(2,4-di-tertamylphenoxy)propyl]-3,5-dioxocyclohexenering etc.

Preference is also given to compounds of formula (1a) wherein

-   R₁ is defined as in formula (1a);-   R₂ is hydrogen;-   R₃ is a cyano group;-   R₄ is —CONHR₅; and-   R₅ is C₁-C₂₂alkyl; or C₆-C₂₀aryl.

If in formula (1a) n=2,

preference is further given to the use of compounds of formula

are used, wherein

-   R₁ is a *—(CH₂)_(m)—* group, not substituted or substituted with one    or more than one C₁-C₅radicals; a bivalent radical of formula

-    a bivalent radical of formula

-    or R₁ and R₂ together with the 2 linking nitrogen atoms form a    bivalent radical of formula (1a₃)

-   R₈ is hydrogen; or C₁-C₅alkyl;-   R₃ is a cyano group; or -Q₁-R₅;-   p is a number form 0 to 3;-   the cyclohexene radical C is not substituted or substituted by one    or more C₁-C₅alkyl; and-   R₂, R₄, R₅, Q₁ and m are defined as in formulae (1a) and (1b).

Preference is further given to the use of compounds of formula

wherein

-   R₁ is a trivalent radical of formula

-   R₂ is hydrogen; or C₁-C₅alkyl;-   R₃ and R₄ independently from each other are a cyano group; or    -Q₁-R₅;-   Q₁ is —COO—; —CONH—; —CO—; —SO₂—; —CONR₁₂—;-   R₅ is C₁-C₅alkyl;-   R₉ and R₁₀ independently from each other are C₁-C₄alkyl;-   R₁₁ and R₁₂ independently from each other are hydrogen; or    C₁-C₅alkyl; and-   p is a number from 0 to 5.

Preference is further given to the use of compounds of formula

wherein

-   R₁ and R₂ are each independently of the other C₁-C₂₂alkyl; or a    cyano group; or R₁ and R₂ together with the nitrogen atom linking    them form a —(CH₂)_(m)— ring which is optionally interrupted by —O—    or by —NR₇—;-   R₄ is a cyano group; or -Q₁-R₅;-   n is 3; or 4;-   if o=3-   R₃ is a trivalent alkyl radical;-   if o=4-   R₃ is a tetravalent alkyl radical;-   R₅, R₇, R₉, R₁₀, Q₁ and m are defined as in formula (1b).

Further preference is given to the use of momomeric, oligomeric orpolymeric compound comprising structural elements of formula

whereinat least one of the asterix-marked radicals may be bound to themomomeric, oligomeric or polymeric radical;the cyclohexene radical C is not substituted or substituted by one ormore C₁-C₅alkyl; and R₂ and R₄ are defined as in formula (1a) and (1b)as UV chromophores.

Preferably, momomeric, oligomeric or polymeric compounds correspond toformula

wherein

Z is a radical of formula (2); R₁₃ is hydrogen; halogen; or C₁-C₅alkyl;R₁₄ is —CONH—; —COO—; or a phenylene radical; R₁₅ is C₁-C₂₀alkylene; orC₆-C₂₀arylene; R₁₆ is —COO—; —OCO—; —CONH—; —NH—CO—O—; —NH—CO—; —SO₂NH—;—NHSO₂—; —SO₂— or —O—;

q is 0; or an integer; andr is 0; or an integer.

The compounds having structural elements of formula (2) are known andare disclosed for example in U.S. Pat. No. 4,749,643, Representatives ofthese compounds are the examples 3.1-3.7 in col. 11-13 in thisreference.

Representatives of these compounds having structural elements of formula(3) are the examples 2.1-2.9 in col. 11-13 of this reference.

Further compounds for use in accordance with the invention are listed inTable MC1 herein below:

TABLE MC1 Com- pound of λ_(max) formula Structure [nm] MC01

366,398(EtOH) MC02

366,398(EtOH) MC03

383(EtOH) MC04

MC05

MC06

MC07

406(EtOH) MC08

373(EtOH) MC09

MC10

384(EtOH) MC11

MC12

MC13

MC14

MC15

MC16

MC17

MC18

388(EtOH) MC19

370(EtOH) MC21

MC21

MC22

MC23

MC24

391(EtOH) MC25

378(EtOH) MC26

MC27

MC28

MC29

MC30

MC31

MC32

MC33

MC34

357/388(EtOH) MC35

389(EtOH) MC36

401(EtOH) MC37

383(Aceto-nitrile)

The merocyanine compounds of formula (1a) and (1b) used in accordancewith the invention are, in some cases, known compounds but also includenovel compounds.

The novel compounds correspond to formula

wherein

-   R′₂ is hydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted or    C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl; a cyano group; or    R₁₁ and R₁₂ together with the nitrogen atom linking them form a    —(CH₂)_(m)— ring which is optionally interrupted by —O— or by    —NR′₇—;-   R′₄ is -Q′₁-R′₅;-   Q′₁ is —COO—; —CONH—; —CO—; —SO₂—; or —CONR′₆—;-   R′₅ is C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; or unsubstituted or    C₁-C₆alkyl-substituted C₆-C₂₀aryl;-   R′₆ is hydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted or    C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl;-   R′₇ is hydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted or    C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl;-   the cyclohexene radical C is not substituted or substituted by one    or more C₁-C₅alkyl;-   m is from 3 to 7;-   n is from 2 to 4;-   o is from 2 to 4;-   if n=2, in formula (1′a)-   R′₁ is an alkylene, cycloalkylene or phenylene-radical; or R′₁ and    R′₂ simultaneously form an alkylene, cycloalkylene or phenylene    radical; and-   R′₃ is a cyano group or -Q′₁-R′₅; or R′₃ and R′₄ together form a 5-    to 7-membered, monocyclic carbocyclic ring;-   If o=2, in formula (1′b)-   R′₃ is an alkylene, cycloalkylene or phenylene radical; and-   R′₁ is hydrogen; a cyano group; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl;    unsubstituted or C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl;    or R₁ and R₂ together with the nitrogen atom linking them form a    —(CH₂)_(m)— ring which is optionally interrupted by —O— or by    —NR′₇—;-   if n=3, in formula (1′a)-   R′₁ is a trivalent alkyl group, which is optionally interrupted by    one or more —O— or —NR′₇-groups; and-   R′₃ is a cyano group or -Q′₁-R′₅; or R′₃ and R′₄ together form a 5-    to 7-membered, monocyclic carbocyclic ring;-   if o=3, in formula (1′b)-   R′₃ is an alkylidene, cycloalkylidene or phenylidene radical; and-   R′₁ is hydrogen; a cyano group; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl;    unsubstituted or C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl;    or R′₁ and R′₂ together with the nitrogen atom linking them form a    —(CH₂)_(m)— ring which is optionally interrupted by —O— or by    —NR₁₇—;-   if n=4, in formula (1′a)-   R′₁ is a tetravalent alkyl group; and-   R′₃ is a cyano group or -Q′₁-R′₅; or R′₃ and R′₄ together form a 5-    to 7-membered, monocyclic carbocyclic ring;-   if o=4, in formula (1b)-   R′₃ is a tetravalent alkyl group; and-   R′₁ is hydrogen; a cyano group; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl;    unsubstituted or C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl;    or R′₁ and R′₂ together with the nitrogen atom linking them form a    —(CH₂)_(m)— ring which is optionally interrupted by —O— or by    —NR′₇—.

The preparation of the compounds of formula (1a) and (1b) may be carriedout according to known methods of the prior art as described for examplein U.S. Pat. No. 4,749,643 on col, 13, line 66-col. 14, line 57 and thereferences cited therein.

The compounds of formula (1a) can be prepared starting from1-aminocyclohexanone-3 of the general formula

wherein R₁, R₂ and n are defined as in formula (1a) by condensation ofdihydroxyresorcines with primary or secondary amine compounds. Afteralkylation with dimethylsulfate or other suitable alkylating agents likediethylsulfate and subsequent reaction with a suitable methylene-activecompound compounds of formula (1a) are obtained.

The alkylation reaction of the starting compounds of formula (3) withsuitable alkylating agents like dimethylsulfate may be carried out in asuitable solvent, preferably dimethylsulfoxide, N-methylpyrrolidone,dimethylformamide or dimethylacetamide. Protic solvents like methanol,ethanol, iso-butanol, tert-butanol or iso-propanol are also suitable.The reaction may also be carried out in aliphatic or aromatic solventslike hexane, toluene or xylol. Ether compounds like diethylether andtetrahydrofurane or halogenated solvents like chloroform ordichlormethane are also suitable solvents as well as mixtures of thesesolvents.

The reaction may be carried out at temperatures between 80° C. and theboiling point of the reaction mixture, preferably from 60 to 120° C.

The intermediates of formula (3), wherein

-   R₂ is hydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted or    C₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl; or R₁ and R₂    together with the nitrogen atom linking them form a —(CH₂)_(m)— ring    which is optionally interrupted by —O— or —NR₃—;-   R₃ is hydrogen; C₁-C₂alkyl; cyclo-C₃-C₈alkyl; or unsubstituted or    C₁-C₆alkyl-substituted C₆-C₂₀aryl;-   m is from 3 to 7;-   n is from 2 to 4;-   the cyclohexene radical C is unsubstituted or substituted by one or    more C₁-C₅alkyl;-   when n=2,-   R₁ and R₂ simultaneously form an alkylene, cycloalkylene or    phenylene radical;-   when n=3,-   R₁ is a trivalent alkyl group, which is optionally interrupted by    one or more —O— or —NR₃-groups;-   when n=4,-   R₁ is a tetravalent alkyl group which is optionally interrupted by    one or more —O— or —NR₃-groups;    are novel and are a further subject matter of the present invention.

They are useful intermediates for the preparation of UV absorbers andrepresent themselves UV-B absorbers for protecting human and animal hairand skin from UV radiation.

Further compounds for use in accordance with the invention are listed inTable MC1a herein below:

TABLE MC1a Com- pound of formula Structure λ_(max) [nm] MC01a

296 (EtOH) MC04a

MC06a

309 (EtOH) MC08a

295(Acetonitril) MC11a

MC12a

MC13a

MC14a

The compounds of the formulae (1a) and (1b) according to the presentinvention are particularly suitable as UV filters, i.e. for protectingultraviolet-sensitive organic materials, in particular the skin and hairof humans and animals, from the harmful effects of UV radiation. Thesecompounds are therefore suitable as sunscreens in cosmetic,pharmaceutical and veterinary medical preparations. These compounds canbe used both in dissolved form and in the micronized state.

The UV absorbers according to the present invention can be used eitherin the dissolved state (soluble organic filters, solubulized organicfilters) or in the micronised state (nanoscalar organic filters,particulate organic filters, UV-absorber pigments).

The merocyanine derivatives of formula (1a) and (1b) which have no alkylsubstituents or only lower-alkyl substituents are characterized by apoor oil-solubility and a high melting point. They are thereforesuitable in particular as UV absorbers in the micronized state.

Any known process suitable for the preparation of microparticles can beused for the preparation of the micronised UV absorbers, for example:wet-milling, wet-kneading, spray-drying from a suitable solvent, by theexpansion according to the RESS process (Rapid Expansion ofSupercritical Solutions), by reprecipitation from suitable solvents,including supercritical fluids (GASR process=Gas Anti-SolventRecrystallisation/PCA process=Precipitation with CompressedAnti-solvents).

The micronised UV absorbers so obtained usually have an average particlesize from 0.02 to 2, preferably from 0.03 to 1.5, and more especiallyfrom 0.05 to 1.0 micrometer.

The UV absorbers according to the present invention can also be used asdry substrates in powder form.

The UV absorbers according to the present invention can also be used inspecific carriers for cosmetics, for example in solid lipidnanoparticles (SLN) or in inert sol-gel microcapsules wherein the UVabsorbers are encapsulated (Pharmazie, 2001 (56), p. 783-786).

The cosmetic formulations or pharmaceutical compositions according tothe present invention may additionally contain one or more than onefurther UV filter.

The cosmetic or pharmaceutical preparations can be prepared byphysically mixing the UV absorber(s) with the adjuvant using customarymethods, for example by simply stirring together the individualcomponents, especially by making use of the dissolution properties ofalready known cosmetic UV absorbers, like octyl methoxy cinnamate,salicylic acid isooctyl ester, etc. The UV absorber can be used, forexample, without further treatment, or in the micronised state, or inthe form of a powder.

Cosmetic or pharmaceutical preparations contain from 0.05-40% by weight,based on the total weight of the composition, of one UV absorber or UVabsorber mixtures.

Preference is given to the use of mixing ratios of the UV absorber offormula (1a) and (1b) according to the present invention and optionallyfurther light-protective agents from 1:99 to 99:1, preferably from 1:95to 95:1 and most preferably from 10:90 to 90:10, based on weight. Ofspecial interest are mixing ratios of from 20:80 to 80:20, preferablyfrom 40:60 to 60:40 and most preferably approximately 50:50. Suchmixtures can be used, inter alia, to improve the solubility or toincrease UV absorption.

Suitable UV filter substances which can be additionally used with the UVabsorbers according to the present invention are for examplep-aminobenzoic acid derivatives, for example 4-dimethylaminobenzoic acid2-ethylhexyl ester; salicylic acid derivatives, for example salicylicacid 2-ethylhexyl ester; benzophenone derivatives, for example2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative;dibenzoylmethane derivatives, for example1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione;diphenylacrylates, for example 2-ethylhexyl2-cyano-3,3-diphenylacrylate, and 3-(benzofuranyl) 2-cyanoacrylate;3-imidazol-4-ylacrylic acid and esters; benzofuran derivatives,especially 2-(p-aminophenyl)-benzofuran derivatives, described inEP-A-582 189, U.S. Pat. No. 5,338,539, U.S. Pat. No. 5,518,713 andEP-A-613 893; polymeric UV absorbers, for example the benzylidenemalonate derivatives described in EP-A-709 080; cinnamic acidderivatives, for example the 4-methoxycinnamic acid 2-ethylhexyl esterand isoamyl ester or cinnamic acid derivatives described in U.S. Pat.No. 5,601,811 and WO 97/00851; camphor derivatives, for example3-(4′-methyl)benzylidene-bornan-2-one, 3-benzylidenebornan-2-one,N-[2(and 4)-2-oxyborn-3-ylidene-methyl)-benzyl]acrylamide polymer,3-(4′-trimethylammonium)-benzylidene-bornan-2-one methyl sulfate,3,3′-(1,4-phenylenedimethine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-methanesulfonicacid) and salts, 3-(4′-sulfo)benzylidene-bornan-2-one and salts;camphorbenzalkonium methosulfate; hydroxyphenyltriazine compounds, forexample2-(4′-methoxyphenyl)-4,6-bis(2′-hydroxy-4′-n-octyloxyphenyl)-1,3,5-triazine;2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-[4-(2-methoxyethyl-carboxyl)-phenylamino]-1,3,5-triazine;2,4-bis{[4-(tris(trimethylsilyloxy-silylpropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(2″-methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(1′,1′,1′,3′,5′,5′,5′-heptamethyltrisilyl-2″-methyl-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-[4-ethylcarboxy)-phenylamino]-1,3,5-triazine;benzotriazole compounds, for example 2,2′-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol;trianilino-s-triazine derivatives, for example 2,4,6-trianiline-(p-carbo-2′-ethyl-1′-oxy)-1,3,5-triazine and the UVabsorbers disclosed in U.S. Pat. No. 5,332,568, EP-A-517 104, EP-A-507691, WO 93/17002 and EP-A-570 838; 2-phenylbenzimidazole-5-sulfonic acidand salts thereof; menthyl o-aminobenzoates; physical sunscreens coatedor not as titanium dioxide, zinc oxide, iron oxides, mica, MnO, Fe2O3,Ce2O3, Al2O3, ZrO2. (surface coatings: polymethylmethacrylate, methicone(methylhydrogenpolysiloxane as described in CAS 9004-73-3), dimethicone,isopropyl titanium triisostearate (as described in CAS 61417-49-0),metal soaps as magnesium stearate (as described in CAS 4086-70-8),perfluoroalcohol phosphate as C9-15 fluoroalcohol phosphate (asdescribed in CAS 74499-44-8; JP 5-86984, JP 4-330007)). The primaryparticle size is an average of 15 nm-35 nm and the particle size indispersion is in the range of 100 nm-300 nm. aminohydroxy-benzophenonederivatives disclosed in DE 10011317, EP 1133980 and EP 1046391phenyl-benzimidazole derivatives as disclosed in EP 1167358; the UVabsorbers described in “Sunscreens”, Eds. N. J. Lowe, N. A. Shaath,Marcel Dekker, Inc., New York and Basle or in Cosmetics & Toiletries(107), 50ff (1992) also can be used as additional UV protectivesubstances.

Preferably, the following UV filter combinations are of specialinterest:

-   -   UV-filter combinations (T) comprising        (t₁) at least one merocyanine derivative of formula (1a) or        (1b); and        (t₂) a triazine compound of formula

wherein

-   R₁ and R₅ are hydrogen; C₁-C₁₈alkyl; or C₆-C₁₂aryl; and-   R₆, R₇ and R₈, independently from each other are hydrogen; hydroxy;    halogen; C₁-C₁₈alkyl; C₁-C₁₈alkoxy; C₆-C₁₂aryl; biphenylyl;    C₆-C₁₂aryloxy; C₁-C₁₈alkylthio; carboxy; —COOM;    C₁-C₁₈-alkylcarboxyl; aminocarbonyl; or mono- or    di-C₁-C₁₈alkylamino; C₁-C₁₀acylamino; or —COOH.

Most preferred are UV-filter combinations comprising

(t₃) the compound of formula (MC02); and(t₄) 1,3,5-Triazine, 2,4,6-tris[1,1′-biphenyl]-4-yl-(9CI).

The compounds of formula (1a) and (1b) may also be used as ananti-wrinkle perception modifier.

The cosmetic or pharmaceutical preparations may be, for example, creams,gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions,wax/fat compositions, stick preparations, powders or ointments. Inaddition to the above mentioned UV filters, the cosmetic orpharmaceutical preparations may contain further adjuvants as describedbelow.

As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/Wemulsions or microemulsions) the preparations contain, for example, from0.1 to 30% by weight, preferably from 0.1 to 15% by weight andespecially from 0.5 to 10% by weight, based on the total weight of thecomposition, of one or more UV absorbers, from 1 to 60% by weight,especially from 5 to 50% by weight and preferably from 10 to 35% byweight, based on the total weight of the composition, of at least oneoil component, from 0 to 30% by weight, especially from 1 to 30% byweight und preferably from 4 to 20% by weight, based on the total weightof the composition, of at least one emulsifier, from 10 to 90% byweight, especially from 30 to 90% by weight, based on the total weightof the composition, of water, and from 0 to 88.9% by weight, especiallyfrom 1 to 50% by weight, of further cosmetically acceptable adjuvants.

The cosmetic or pharmaceutical compositions/preparations according tothe invention may also contain one or one more additional compounds likefatty alcohols, esters of fatty acids, natural or synthetictriglycerides including glyceryl esters and derivatives, pearlescentwaxes, hydrocarbon oils, silicones or siloxanes (organosubstitutedpolysiloxanes), fluorinated or perfluorinated oils, emulsifiers,super-fatting agents, surfactants, consistency regulators/thickeners andrheology modifiers, polymers, biogenic active ingredients, deodorizingactive ingredients, anti-dandruff agents, antioxidants, hydrotropicagents, preservatives and bacteria-inhibiting agents, perfume oils,colorants, polymeric beads or hollow spheres as SPF enhancers,

Cosmetic or Pharmaceutical Preparations

Cosmetic or pharmaceutical formulations are contained in a wide varietyof cosmetic preparations. There come into consideration, for example,especially the following preparations: skin-care preparations, bathpreparations, cosmetic personal care preparations, foot-carepreparations, light-protective preparations, skin-tanning preparations,depigmenting preparations, deodorants, antiperspirants, preparations forcleansing and caring for blemished skin, shaving preparations, fragrancepreparations or cosmetic hair-treatment preparations

Of special importance as cosmetic preparations for the skin arelight-protective preparations, such as sun milks, lotions, creams, oils,sunblocks or tropicals, pretanning preparations or after-sunpreparations, also skin-tanning preparations, for example self-tanningcreams. Of particular interest are sun protection creams, sun protectionlotions, sun protection milk and sun protection preparations in the formof a spray.

The cosmetic preparation according to the invention is characterized byexcellent protection of human skin against the damaging effect ofsunlight.

PREPARATION EXAMPLES Example 1 Preparation of the Compound MC 20

1a. Preparation of the Preliminary Stage (Compound MC 01a)

A mixture of 6.04 g ethylenediamine and 31.15 g dimedone in 200 mltoluene is heated under reflux conditions using a water separator forthree hours.

After cooling down the mixture the product is filtered off, washed withminor amounts of ethyl acetate and dried in vacuum at 80° C.

The yield is nearly quantitative.

Mp. ≧250° C.

Example 1b Preparation of the Compound MC2

7.61 g of the compound MC14a are dissolved in 375 ml N-methylpyrrolidoneat 100° C. and mixed dropwise with 6.50 g dimethylsulfate.

The reaction mixture is stirred for 60 minutes at 100° C.

After cooling down to 80° C. a mixture of 5.81 g cyan acidicacidethylester, 5.14 g triethylamine and 4.3 ml isopropanol is addedslowly dropwise. The reaction mixture is stirred at a temperature of100° C. for 90 minutes.

After cooling down of the reaction mixture the raw product is filteredoff.

Subsequent column chromatography with a mixture of toluene and methanol(6:4) over silica gel delivers 1.28 g (10% o. th.) of a pure productwhich is dried in vacuum at 80° C.

λ_(max) (acetonitril)=389 nm.

Example 2a Preparation of Compound MC06a

A mixture of 9.06 g dimedone and 2.78 g piperazine in 64 ml toluene isheated under reflux conditions using a water separator for five hours.

After cooling down the mixture the product is filtered off, washed withminor amounts of ethyl acetate and dried in vacuum at 80° C. Yield: 75%.

Example 2b Preparation of the Compound MC07

3.34 g dimethylsulfate are added dropwise to 4.33 g of the compound MC06a (prepared in Example 2a). The reaction mixture is stirred for 60minutes at 100° C.

After cooling down to 80° C. a mixture of 2.89 g ethyl cyano acetate and5.21 g of triethylamine is added dropwise. The reaction mixture isstirred at a temperature of 110° C. for 90 minutes.

After cooling down and the addition of 300 ml water the raw product isfiltered off. Subsequent column chromatography with a mixture of tolueneand methanol (6:4) over silica gel delivers 4.5 g (65% o. th.) of a pureproduct, which is dried in vacuum at 80° C.

λ_(max) (ethanol)=406 nm.

Example 3a Preparation of Compound MC08a

A mixture of 9.06 g dimedone and 4.30 g 1,2-diamino-cyclohexane in 64 mltoluene is heated under reflux conditions using a water separator forthree hours.

After cooling down the mixture the product is filtered off, washed withminor amounts of ethyl acetate and dried in vacuum at 80° C. yielding95% product.

Example 3b Preparation of the Compound MC10

22.86 g of dimethylsulfate are added dropwise to 16.99 g of the compoundMC 06a. The reaction mixture is stirred for 60 minutes at 100° C.

After cooling down to 80° C. the mixture is treated with 13.50 g oftriethylamine and stirred for 10 minutes. Then a mixture of 16.72 gdiethylmalonate and 28.89 g DBU is added slowly dropwise. The reactionmixture is stirred at a temperature of 100° C. for 90 minutes.

After cooling down and the addition of 300 mL of water the raw productis filtered off. Subsequent column chromatography with a mixture oftoluene and methanol (6:4) over silica gel delivers 21.28 g (70% o. th.)of a pure product which is dried in vacuum at 80° C.

λ_(max) (ethanol)=373 nm.

Example 3c Preparation of the Compound MC09

17.93 g (0.05 mol) MC09a are heated with 30 ml dimethylsulfate in an oilbath up to 100° C. and stirred for 40 min at this temperature. Thereaction mixture is cooled down to 60° C., a mixture of 11.93 g (0.103mol) ethyl cyano acetate and 8.25 g (0.120 mol) sodium ethanolate areadded in 50 ml ethanol and stirred for 40 minutes at 110° C., whereinethanol is distilled off during the reaction. The mixture is cooleddown, the compound precipitated with H₂O and extracted by suction.

The subsequent column chromatography (Kieselgel) with a 9:1-mixture oftoluene and acetone delivers the pure product which is dried in vacuumat 80° C.

Yield: 23.3 g (85% d. Th.).

Example 4 Preparation of Micronized UV Absorbers

100 parts of the compound of formula MC 2 are milled together withzirconium silicate bells (diameter: 0.1 to 4 mm) as grinding aids, adispersing agent (15 parts of C₈-C₁₆polyglucoside) and water (85 parts)in a ball mill to a mean particle size of d₅₀=200 nm. With this method amicropigment dispersion of a UV absorber is obtained.

APPLICATION EXAMPLES Example 5 UV-A/UV-B Daily Care UV Protection Lotion

% w/w INCI-Name (as supplied) Part A Oleth-3 Phosphate 0.60 Steareth-212.50 Steareth-2 1.00 Cetyl Alcohol 0.80 Stearyl Alcohol 1.50 Tribehenin0.80 Isohexadecane 8.00 Ethylhexyl Methoxycinnamate 5.00 Part B Water qsto 100 Glycerin 2.00 UV-absorber dispersion as described in example 43.00 Disodium EDTA 0.10 Part C Water 20.00  Diazolidinyl Urea (and)Iodopropynyl 0.15 Butylcarbamate Propylene Glycol 4.00 Part D SodiumAcrylates Copolymer (and) 1.50 Paraffinium Liquidum (and) PPG-1Trideceth-6 Cyclopentasiloxane 4.50 PEG-12 Dimethicone 2.00 TocopherylAcetate 0.45 Water (and) Citric Acid qs Part E Fragrance qs

Manufacturing Instruction:

Part A and part B are heated separately to 75° C. Part A is poured intopart B under continuous stirring. Immediately after the emulsification,Cyclopentasiloxane and PEG-12 Dimethicone from part D are incorporatedinto the mixture. Afterwards the mixture is homogenized with an UltraTurrax at 11 000 rpm for 30 sec. After cooling down to 65° C. SodiumAcrylates Copolymer (and) Paraffinium Liquidum (and) PPG-1 Trideceth-6are incorporated. Part C is added at a temperature <50° C. At atemperature <35° C. Tocopheryl Acetate is incorporated and subsequentlythe pH is adjusted with Water (and) Citric Acid. At room temperaturepart E is added.

Example 6 UV Day Lotion

% w/w INCI-Name (as supplied) Part A Cetyl Phosphate 1.75 C12-C15 AlkylBenzoate 5.00 Cetearyl Alcohol/PEG-20 Stearate 2.00 EthoxydiglycolOleate 2.00 Stearic Acid 1.50 Ethylhexyl Methoxycinnamate 3.00 IsononylIsononanoate 2.00 Part B Aqua qs to 100 Xanthan Gum 0.35 UV-absorberdispersion as described in example 4 5.00 Disodium EDTA 0.20 PropyleneGlycol 2.00 Diazolidinyl Urea (and) Methylparaben 0.70 (and)Propylparaben (and) Propylene Glycol Glycerin 1.50 Part CCyclopentasiloxane (and) Dimethiconol 1.00 Ethoxydiglycol 3.00Dimethicone 2.00 Part D Triethanolamine qs

Manufacturing Instruction:

Part A is prepared by incorporating all ingredients, then stirred undermoderate speed and heated to 75° C. Part B is prepared and heated to 75°C. At this temperature part B is poured into part A under progressivestirring speed. Then the mixture is homogenized (30 sec., 15000 rpm). Ata temperature <55° C. the ingredients of part C are incorporated. Themixture is cooled down under moderate stirring, then the pH is checkedand adjusted with triethanolamine.

Example 7 Sun Protection Emulsion

% w/w INCI-Name (as supplied) Part A Cetearyl Alcohol (and) DicetylPhosphate10 4.00 (and) Ceteth-Phosphate C12-15 Alkyl Benzoate 2.00Dicaprylyl Ether 3.00 Ethoxydiglycol Oleate 2.00 Stearic Acid 1.00Ethylhexyl Methoxycinnamate 3.00 Sodium Acrylates Copolymer (and)Glycine1 0.30 Soja (and) PPG-Trideceth-6 Squalane 3.50 Part B Aqua qs to100 UV-absorber dispersion as described in example 4 5.00 Part CDiazolidinyl Urea (and) Iodopropynyl 0.15 Butylcarbamate PropyleneGlycol 2.50 Aqua 10.00  Part D Cyclopentasiloxane, Dimethiconol 2.00Ethoxydiglycol 5.00 Cyclopentasiloxane (and) Dimethicone/Vinyl- 2.00dimethicone Crosspolymer Part E Sodium Hydroxide 0.10

Manufacturing Instruction:

Part A is prepared by incorporating all ingredients, then stirred undermoderate speed and heated to 75° C. Part B is prepared and heated to 75°C. At this temperature, part B is poured into part A under progressivestirring speed. Below 65° C. the ingredients of part D are addedseparately. After cooling down under moderate stirring to 55° C. part Cis added. The pH is then checked and adjusted with sodium hydroxide. Themixture is homogenized for 30 sec at 16000 rpm.

Example 8 Every Day Lotion

% w/w INCI-Name (as supplied) Part A Stearyl Phosphate 5.00 TricontanylPVP 1.00 Ethoxydiglycol Oleate 3.00 Squalane 5.00 C12-15 Alkyl Benzoate5.00 Ethylhexyl Methoxycinnamate 3.00 Glyceryl Stearate 2.00 CetylAlcohol 2.00 Part B Aqua 20.00  UV-absorber dispersion as described inexample 4 3.00 Part C Aqua qs to 100 Steareth-10 Allyl Ether/AcrylatesCopolymer 0.50 Glycerin 2.50 Diazolidinyl Urea (and) Iodopropynyl 0.15Butylcarbamate Sodium Lauroyl Glutamate 0.70 Part D Cyclopentasiloxane(and) Dimethiconol 1.50 Triethanolamine 1.85

Manufacturing Instruction:

Part A is prepared by incorporating all ingredients, then stirred undermoderate speed and heated to 75° C. Part C is prepared and heated to 75°C. Part C is poured into the part A under moderate stirring. Immediatelyafter the emulsification part B is added, then neutralized with a partof the triethanolamine. The mixture is homogenized for 30 sec. Aftercooling down under moderate stirring Cyclopentasiloxane (and)Dimethiconol are added. Below 35° C. the pH is checked and adjusted withtriethanolamine.

Example 9 Sprayable Sunscreen Emulsion

% w/w INCI-Name (as supplied) Part A Ceteareth-15 (and) GlycerylStearate 3.00 Stearyl Alcohol 1.00 Cetyl Ricinoleate 0.80 DicaprylylEther 3.00 C12-15 Alkyl Benzoate 3.00 Isohexadecane 2.50 StearylDimethicone 1.00 Ethylhexyl Methoxycinnamate 4.00 Cetyl Alcohol 0.80Di-C12-13 Alkyl Tartrate 3.00 Part B Aqua qs to 100 Steareth-10 AllylEther/Acrylates Copolymer 0.45 PEG-7 Glyceryl Cocoate 2.50 Glycerin 2.00Propylene Glycol 3.00 Part C Diazolidinyl Urea (and) Iodopropynyl 0.15Butylcarbamate Aqua 20.00  UV-absorber dispersion as described inexample 4 12.00  Titanium Dioxide (and) Silica (and) Sodium 8.00Polyacrylate Part D Cyclopentasiloxane (and) Dimethiconol 0.85 Part ESodium Hydroxide (and) Water qs to pH 6.50-7.00 Part F Fragrance qs

Manufacturing Instruction

Part A and part B are heated up to 80° C. Part A is blended into part Bunder stirring and homogenized with an Ultra Turrax at 11 000 rpm for 30sec. Part C is heated to 60° C. and added slowly to the emulsion. Aftercooling down to 40° C. part D is incorporated at room temperature andpart E is added.

Example 10 Daily Care Lotion

% w/w INCI-Name (as supplied) Part A Polyglyceryl Methyl GlucoseDistearate 2.50 Cetearyl Alcohol 2.00 Octyl Stearate 3.00Caprylic/Capric Triglyceride 4.00 Isohexadecane 4.00 EthylhexylMethoxycinnamate 2.70 Part B Aqua 64.80 Glycerin 5.00 Phenoxyethanol(and) Methylparaben (and) 0.50 Butylparaben (and) Ethylparaben (and)Propylparaben UV-absorber dispersion as described in example 4 8.00 PartC Cyclomethicone (and) Dimethicone 3.00 Part D Steareth-10 AllylEther/Acrylates Copolymer 0.50

Manufacturing Instruction

Part A and B are heated to 75° C. Part A is added into part B undercontinuous stirring and homogenized with 11000 rpm for 1 minute. Aftercooling down to 50° C. part C is added under continuous stirring. Aftercooling further down to 30° C. part D is added. Afterwards the pH isadjusted between 6.00-6.50.

Example 11 Daily Care with UV Protection

% w/w INCI-Name (as supplied) Part A Glyceryl Stearate SE 3.00 GlycerylStearate and PEG-100 Stearate 3.50 Cetyl Alcohol 1.50 Myristyl Myristate2.00 Isopropyl Palmitate 2.50 Paraffinum Perliquidum 5.00 Octyl DimethylPABA 3.00 Part B Aqua qs to 100 Propylene Glycol 7.50 Phenoxyethanol(and) Methylparaben (and) 1.00 Butylparaben (and) Ethylparaben (and)Propylparaben Part C Aqua 30.00  UV-absorber dispersion as described inexample 4 10.00  Part D Sodium Acrylates Copolymer (and) Paraffinium2.00 Liquidum (and) PPG-1 Trideceth-6 Part E Citric Acid 0.30

Manufacturing Instruction:

Part A and B are heated separately to 75° C. After adding part B intopart A the mixture is homogenized with Ultra Turrax for one minute at11000 rpm. After cooling down to 50° C. part C is added. Afterwards themixture is homogenized for one minute at 16000 rpm. At a temperature<40° C. part D is added. At room temperature the pH-value is adjustedwith part E between 6.00 and 6.50.

Example 12 O/W Every Day UV Protection Lotion

% w/w INCI-Name (as supplied) Part A Glyceryl Stearate (and) PEG-100Stearate 5.00 Stearyl Alcohol 1.00 Tripalmitin 0.70 Dimethicone 2.00C12-15 Alkyl Benzoate 5.00 Isopropyl Palmitate 5.00 EthylhexylMethoxycinnamate 3.00 Part B Water qs to 100 Polysorbate 60 0.50Glycerin 3.00 Part C Water 10.00 UV-absorber dispersion as described inexample 4 8.00 Part D Phenoxyethanol (and) Methylparaben (and) 0.70Ethylparaben (and) Butylparaben (and) Propylparaben (and)Isobutylparaben Steareth-10 Allyl Ether/Acrylates Copolymer 1.50 Part EWater (and) Sodium Hydroxide qs Phenoxyethanol (and) Methylparaben (and)1.00 Butylparaben (and) Ethylparaben (and) Propylparaben Part C Aqua30.00 UV-absorber dispersion as described in example 4 10.00 Part DSodium Acrylates Copolymer (and) Paraffinium 2.00 Liquidum (and) PPG-1Trideceth-6 Part E Citric Acid 0.30

Manufacturing Instruction:

Part A and B are heated separately to 75° C. After adding part B intopart A the mixture is homogenized with Ultra Turrax for one minute at11000 rpm. After cooling down to 50° C. part C is added. Afterwards themixture is homogenized for one minute at 16000 rpm. At a temperature<40° C. part D is added. At room temperature the pH-value is adjustedwith part E between 6.00 and 6.50.

Example 12 O/W Every Day UV Protection Lotion

% w/w INCI-Name (as supplied) Part A Glyceryl Stearate (and) PEG-100Stearate 5.00 Stearyl Alcohol 1.00 Tripalmitin 0.70 Dimethicone 2.00C12-15 Alkyl Benzoate 5.00 Isopropyl Palmitate 5.00 EthylhexylMethoxycinnamate 3.00 Part B Water qs to 100 Polysorbate 60 0.50Glycerin 3.00 Part C Water 10.00  UV-absorber dispersion as described inexample 4 8.00 Part D Phenoxyethanol (and) Methylparaben (and) 0.70Ethylparaben (and) Butylparaben (and) Propylparaben (and)Isobutylparaben Steareth-10 Allyl Ether/Acrylates Copolymer 1.50 Part EWater (and) Sodium Hydroxide qs Part F Fragrance qs

Manufacturing Instruction:

Part A and B are heated separately up to 75° C., part C is heated to 60°C. Afterwards part B is poured into part A under stirring. The mixtureis homogenized with an Ultra Turrax for 30 sec. at 11 000 rpm and part Cis incorporated. After cooling down to 40° C. part D is added. At roomtemperature the pH-value is adjusted with Sodium Hydroxide between 6.30and 6.70 and part F is added.

Example 13 O/W Every Day UV Protection

% w/w INCI-Name (as supplied) Part A Glyceryl Stearate (and) PEG-100Stearate 5.00 Stearyl Alcohol 1.00 Tripalmitin 0.70 Dimethicone 2.00C12-15 Alkyl Benzoate 5.00 Isopropyl Palmitate 5.00 EthylhexylMethoxycinnamate 3.00 Part B Water qs to 100 Polysorbate 60 0.50Glycerin 3.00 Part C Water 10.00  UV-absorber dispersion as described inexample 4 8.00 Part D Phenoxyethanol (and) Methylparaben (and) 0.70Ethylparaben (and) Butylparaben (and) Propylparaben (and)Isobutylparaben Steareth-10 Allyl Ether/Acrylates Copolymer 1.50 Part EWater (and) Sodium Hydroxide qs Part F Fragrance qs

Manufacturing Instruction:

Part A and B are heated separately up to 75° C., part C is heated to 60°C. Afterwards part B is poured into part A under stirring. The mixtureis homogenized with an Ultra Turrax for 30 sec. at 11 000 rpm and part Cis incorporated. After cooling down to 40° C. part D is added. At roomtemperature the pH-value is adjusted with Sodium Hydroxide between 6.30and 6.70 and part F is added.

Example 14 Sunscreen Cream

% w/w INCI-Name (as supplied) Part A Cetearyl Alcohol (and) DicetylPhosphate 4.50 (and) Ceteth-10 Phosphate C12-15 Alkyl Benzoate 6.00Caprylic/Capric Triglyceride 7.00 Pentaerythritol Tetraisostearate 2.00Ethylhexyl Methoxycinnamate 3.00 Isoamyl p-Methoxycinnamate 2.00 Part BAqua qs to 100 Glycerin 2.00 Propylene Glycol 1.50 Magnesium AluminiumSilicate 1.20 Part C Steareth-10 Allyl Ether/Acrylates Copolymer 0.50UV-absorber dispersion as described in example 4 12.00  Part D PhenylTrimethicone 1.50 Phenoxyethanol (and) Methylparaben (and) 0.70Butylparaben (and) Ethylparaben (and) Propylparaben Part E SodiumHydroxide 0.90

Manufacturing Instruction:

Part A and part B are heated separately to 75° C. Part B is added intopart A under continuous stirring and afterwards homogenized with UltraTurrax for 30 sec at 11000 rpm. After cooling down to 60° C. part C isadded. At 40° C. part C is added and homogenized for 15 sec at 11000rpm. At room temperature the pH-value is adjusted with part E.

Example 15 UVA/UVB Daily Care Lotion, Type O/W

% w/w INCI-Name (as supplied) Part A Glyceryl Stearate (and) PEG-100Stearate 5.00 Stearyl Alcohol 1.00 Tripalmitin 0.70 Mineral Oil 15.00 Part B Water qs to 100 Polysorbate 60 0.50 Glycerin 3.00 Part C Water10.00  UV-absorber dispersion as described in example 4 8.00 Part DSteareth-10 Allyl Ether/Acrylates Copolymer 1.50 Phenoxyethanol (and)Methylparaben (and) 0.70 Ethylparaben (and) Butylparaben (and)Propylparaben (and) Isobutylparaben Part E Water (and) Sodium Hydroxideqs Part F Fragrance qs

Manufacturing Instruction:

Part A and B are heated separately to 75° C.; part C to 60° C. Part B ispoured into part A under stirring. After one-minute of homogenization at11000 rpm part C is added to the mixture of A/B. After cooling down to40° C. part D is incorporated. At room temperature the pH value isadjusted with part E between 6.3 and 7.0. Finally part F is added.

Example 16 UVA/UVB Daily Care Lotion, Type O/W

% w/w INCI-Name (as supplied) Part A Oleth-3 Phosphate 0.60 Steareth-212.50 Steareth-2 1.00 Cetyl Alcohol 0.80 Stearyl Alcohol 1.50 Tribehenin0.80 Isohexadecane 8.00 Part B Water qs to 100 Glycerin 2.00 DisodiumEDTA 0.10 Part C Cyclopentasiloxane 4.50 PEG-12 Dimethicone 2.00 Part DSodium Acrylates Copolymer (and) Mineral 1.50 Oil (and) PPG-1Trideceth-6 Part E UV-absorber dispersion as described in example 410.00  Part F Tocopheryl Acetate 0.45 DMDM Hydantoin (and) Iodopropynyl0.85 Butylcarbamate (and) Aqua (and) Butylene Glycol Part G Water (and)Citric Acid qs Fragrance qs

Manufacturing Instruction:

Part A and part B are heated separately to 75° C. Part A is poured intopart B under stirring. Immediately after the emulsification, part C isadded to the mixture and homogenized with an Ultra Turrax at 11000 rpmfor 30 sec. After cooling down to 65° C. Sodium Acrylates Copolymer(and) Mineral Oil (and) PPG-1 Trideceth-6 At 50° C. is added slowly tothe UV absorber dispersion. At about 35-30° C. part F is incorporated.The pH is adjusted with part G between 5.5 and 6.5.

Example 17 UV-A/UV-B Every Day Protection Lotion O/W

% w/w INCI-Name (as supplied) Part A Glyceryl Dilaurate 2.00 EthylhexylPalmitate 6.00 Cetyl Alcohol 1.00 Glyceryl Stearate 2.00 Laureth-23 1.00Isopropyl Palmitate 2.00 Tribehenin 0.80 Beeswax 1.50 Lanolin Oil 1.00Part B Water qs to 100 Propylene Glycol 4.00 Water (and) TitaniumDioxide (and) Alumina 4.00 (and) Sodium Meta-phosphate (and)Phenoxyethanol (and) Sodium Methylparaben Part C Steareth-10 AllylEther/Acrylates Copolymer 1.00 Part D Phenoxyethanol (and) Methylparaben(and) 1.00 Ethylparaben (and) Butylparaben (and) Propylparaben (and)Isobutylparaben UV-absorber dispersion as described in example 4 8.00Part E Water (and) Sodium Hydroxide qs

Manufacturing Instruction:

Part A and part B are heated separately up to 80° C. Part A is pouredinto part B while stirring and homogenized with an Ultra Turrax by 11000rpm for 30 sec. After cooling down to 60° C. part C is incorporated. At40° C. part D is added slowly under continuous stirring. The pH isadjusted with part E between 6.50-7.00.

Example 18 Sprayable Sunscreen Lotion

% w/w INCI-Name (as supplied) Part A Potassium Cetyl Phosphate 0.20Isohexadecane 7.00 VP/Eicosene Copolymer 1.50 Di-C12-13 Alkyl Tartrate6.00 Ethylhexyl Triazone 2.50 C12-15 Alkyl Benzoate 4.50 Part B Water qsto 100 Sorbeth-30 2.00 Sorbitan Stearate (and) Sucrose Cocoate 4.00Titanium Dioxide (and) Alumina (and) Silica 2.50 (and) SodiumPolyacrylate Part C Water 30.00  UV-absorber dispersion as described inexample 4 12.00  Part D Phenoxyethanol (and) Methylparaben (and) 0.70Ethylparaben (and) Butylparaben (and) Propylparaben (and)Isobutylparaben Part E Water (and) Citric Acid qs

Manufacturing Instruction:

Part A and part B are heated separately up to 80° C., part C is heatedto 50° C. Part B is poured into part A and homogenized with an UltraTurrax for 1 minute at 11000 rpm. After cooling down to 50° C. part C isadded under continuous stirring. At 40° C. part D is incorporated andhomogenized again for 10 sec. at 11000 rpm. The pH is adjusted with partE.

Example 19 O/W Every Day UV Protection Lotion

% w/w INCI-Name (as supplied) Part A Glyceryl Stearate (and) PEG-100Stearate 5.00 Stearyl Alcohol 1.00 Tripalmitin 0.70 Dimethicone 2.00Caprylic/Capric Triglyceride 5.00 Isopropyl Palmitate 5.00 EthylhexylMethoxycinnamate 3.00 Part B Water qs to 100 Polysorbate 60 0.50Glycerin 3.00 Part C Water 10.00  UV-absorber dispersion as described inexample 4 8.00 Part D Phenoxyethanol (and) Methylparaben (and) 0.70Ethylparaben (and) Butylparaben (and) Propylparaben (and)Isobutylparaben Steareth-10 Allyl Ether/Acrylates Copolymer 1.50 Part EWater (and) Sodium Hydroxide qs Part F Fragrance qs

Manufacturing Instruction:

Part A and part B are heated separately up to 75° C., part C is heatedto 60° C. Afterwards part B is poured into part A under stirring. Themixture is homogenized with an Ultra Turrax for 30 sec. at 11 000 rpmand part C is incorporated. After cooling down to 40° C. part D isadded. At room temperature the pH-value is adjusted with SodiumHydroxide between 6.30 and 6.70 and part F is added.

Example 20 Water Resistant Sunscreen Emulsion

% w/w INCI-Name (as supplied) Part A Polyglyceryl-10 Pentastearate (and)Behenyl 2.50 Alcohol (and) Sodium Stearoyl Lactylate VP/EicoseneCopolymer 1.50 Stearyl Alcohol 1.50 Squalane 4.00 C12-15 Alkyl Benzoate7.50 Octocrylene 1.50 4-Methylbenzylidene Camphor 3.00 EthylhexylMethoxycinnamate 2.00 Part B Water qs to 100 Glycerin 1.80 Steareth-10Allyl Ether/Acrylates Copolymer 0.80 Part C UV-absorber dispersion asdescribed in example 4 9.00 Part D VP/Hexadecene Copolymer 2.70Cyclomethicone 1.50 Phenoxyethanol (and) Methylparaben (and) 0.70Ethylparaben (and) Butylparaben (and) Propylparaben (and)Isobutylparaben Part E Aqua (and) Tocopheryl Acetate (and) Caprylic/3.50 Capric Triglyceride (and) Polysorbate 80 (and) Lecithin Part FFragrance qs Water (and) Sodium Hydroxide qs

Manufacturing Instruction:

Part A and part B are heated separately to 80° C. Part A is poured intopart B under continuous stirring. Afterwards the mixture is homogenizedwith an Ultra Turrax at 11 000 rpm for 1 min. After cooling down to 60°C. part C is incorporated. At 40° C. part D is added and the mixturehomogenized for a short time again. At 35° C. part E is added and atroom temperature Fragrance is added. Finally the pH is adjusted withSodium Hydroxide.

Example 21 UVA/UVB Sun Protection Lotion, O/W Type

% w/w INCI-Name (as supplied) Part A Potassium Cetyl Phosphate 2.00Tricontanyl PVP 1.00 Caprylic/Capric Triglyceride 5.00 C12-15 AlkylBenzoate 5.00 Cetearyl Isononanoate 5.00 Glyceryl Stearate 3.00 CetylAlcohol 1.00 Dimethicone 0.10 Ethylhexyl Methoxycinnamate 5.00 Part BWater qs to 100 Glycerin 3.00 Part C Steareth-10 Allyl Ether/AcrylatesCopolymer 0.50 Part D UV-absorber dispersion as described in example 48.00 Part E Phenoxyethanol (and) Methylparaben (and) 1.00 Ethylparaben(and) Butylparaben (and) Propylparaben (and) Isobutylparaben Part FWater (and) Sodium Hydroxide qs to pH 7.00 Part G Fragrance qs

Manufacturing Instruction:

Part A and part B are heated separately up to 80° C. Part B is pouredinto part A under moderate stirring. The mixture is homogenized with anUltra Turrax at 11000 rpm for 1 minute. After cooling down to 70° C.part C is added under stirring. After cooling further down to 50° C.part D is incorporated very slowly. At 40° C. part E is added. At roomtemperature the pH is adjusted with part F to 7.00 and part G is added.

Example 22 UVA/UVB Sun Protection Lotion, O/W Type

% w/w INCI-Name (as supplied) Part A Potassium Cetyl Phosphate 2.00Tricontanyl PVP 1.00 Caprylic/Capric Triglyceride 5.00 C12-15 AlkylBenzoate 5.00 Cetearyl Isononanoate 5.00 Glyceryl Stearate 3.00 CetylAlcohol 1.00 Dimethicone 0.10 Ethylhexyl Methoxycinnamate 5.00 Part BWater qs to 100 Glycerin 3.00 Part C Steareth-10 Allyl Ether/AcrylatesCopolymer 0.50 Part D UV-absorber dispersion as described in example 420.00  Part E Phenoxyethanol (and) Methylparaben (and) 1.00 Ethylparaben(and) Butylparaben (and) Propylparaben (and) Isobutylparaben Part FWater (and) Sodium Hydroxide qs to pH 7.00 Part G Fragrance qs

Manufacturing Instruction:

Part A and part B are heated separately up to 80° C. Part B is pouredinto part A under moderate stirring. The mixture is homogenized with anUltra Turrax at 11000 rpm for 1 minute. After cooling down to 70° C. addpart C is added under stirring. After cooling further down to 50° C.part D is incorporated very slowly. At 40° C. part E is added. At roomtemperature the pH is adjusted with part F to 7.00 and part G is added.

Example 23 Sunscreen Lotion

% w/w INCI-Name (as supplied) Part A Cetearyl Alcohol (and) DicetylPhosphate (and) 4.00 Ceteth-10 Phosphate C12-15 Alkyl Benzoate 2.00Dicaprylyl Ether 3.00 Ethoxydiglycol Oleate 2.00 Stearic Acid 1.00Ethylhexyl Methoxycinnamate 3.00 Sodium Acrylates Copolymer (and)Glycine Soja 0.30 (and) PPG-1 Trideceth-6 Squalane 3.50 VP/EicoseneCopolymer 2.00 Part B Water qs to 100 UV-absorber dispersion asdescribed in example 4 5.00 Part C Diazolidinyl Urea (and) Iodopropynyl0.15 Butylcarbamate Propylene Glycol 2.50 Water 10.00  Part DCyclopentasiloxane (and) Dimethiconol 2.00 Ethoxydiglycol 5.00Cyclopentasiloxane (and) Dimethicone/Vinyl 2.00 Dimethicone CrosspolymerPart E Aqua (and) Sodium Hydroxide qs Part F Fragrance qs

Manufacturing Instruction

Part A and part B are heated separately up to 75° C. Part B is pouredinto part A under progressive stirring speed. At a temperature <65° C.the ingredients of part D are added separately. After cooling down to55° C. under moderate stirring part C is added. At a temperature <35° C.the pH is checked and adjusted with Sodium Hydroxide and homogenizedwith an Ultra Turrax for 30 sec. at 11 000 rpm. Part F is added at roomtemperature.

Example 24 W/O Sunscreen Lotion

% w/w INCI-Name (as supplied) Part A PEG-7 Hydrogenated Castor Oil 3.00Polyglyceryl-3 Diisostearate 4.00 Microcrystalline Wax 1.00 MagnesiumStearate 1.50 Propylparaben 0.10 Mineral Oil 15.00  Octyldodecanol 8.00Ethylhexyl Triazone 1.00 Ethylhexyl Methoxycinnamate 2.00 Part B Waterqs to 100 Water (and) Citric Acid 0.05 Methylparaben 0.15 MagnesiumSulfate 0.50 Part C UV-absorber dispersion as described in example 49.00 Fragrance qs

Manufacturing Instruction:

Part A is heated to 80° C. whilst stirring. Part B is added into part Aand homogenized with an Ultra Turrax at 11 000 rpm for one minute. Aftercooling down to 30° C. part C is incorporated.

Example 25 Skin Protection Sunscreen Lotion W/O

% w/w INCI-Name (as supplied) Part A Polyglyceryl-2Dipolyhydroxystearate 3.00 Glyceryl Oleate 3.00 Cetearyl Isononanoate7.00 Hexyl Laurate 6.00 Dicaprylyl Ether 6.00 Propylparaben 0.10Hexyldecanol 3.00 Magnesium Stearate 1.00 Beeswax 1.00 EthylhexylMethoxycinnamate 4.00 Part B Water qs to 100 Methylparaben 0.15Magnesium Sulfate 1.00 Part C UV-absorber dispersion as described inexample 4 6.00

Manufacturing Instruction:

Part A is heated separately to 80° C. under gentle stirring. Part B isadded to part A and homogenized for one minute at 11000 rpm. Aftercooling down to 30° C. part C is added under continuous stirring.

Example 26 O/W Emulsion

% w/w INCI-Name (as supplied) Part A UV absorber of formula (MC10) 3 gsesame oil 10 g glyceryl stearate 4 g stearic acid 1 g cetyl alcohol 0.5g polysorbate 20 0.2 g Part B propylene glycol 4 g propylparaben 0.05 gmethylparaben 0.15 g triethanolamine 0.1 g carbomer 934 0.1 g water ad100 ml

Preparation of the Emulsion Phase (A):

Firstly, the UV absorber is dissolved in sesame oil. The othercomponents of (A) are added thereto and combined.

Phase (B):

Propylparaben and methylparaben are dissolved in propylene glycol. 60 mlof water are then added, heating to 70° C. is carried out and thencarbomer 934 is emulsified therein.

Emulsion:

(A) is slowly added to (B) with vigorous application of mechanicalenergy. The volume is adjusted to 100 ml by the addition of water.

Example 27 Daily Care Cream, Type O/W

% w/w INCI name (as used) Part A Glyceryl stearate (and) cetearylalcohol (and) 4.0 cetyl palmitate (and) cocoglycerides Ceteareth-12 4.0Cetearyl alcohol 2.0 Dicaprylyl ether 4.5 Ethylhexyl stearate 4.0 Hexyllaurate 3.5 Ethylhexyl triazone 1.0 Benzylidene malonate polysiloxane2.0 HDI/trimethylol hexyl-lactone crosspolymer (and) 5.0 silica Stearyldimethicone 1.0 Dimethicone 2.0 Cetyl alcohol 0.8 compound of formula(MC10) 2.0 Part B Water q.s. to 100 Water (and) scleroglucan (and)phenoxyethanol 2.0 Glycerol 2.0 Part C Steareth-10 allyl ether/acrylatecopolymer  0.45 Phenoxyethanol (and) methylparaben (and) 0.7ethylparaben (and) butylparaben (and) propylparaben (and)isobutylparaben Part D Aqua (and) tocopheryl acetate (and)caprylic/capric 4.0 triglyceride (and) polysorbate 80 (and) lecithinPart E Water (and) sodium hydroxide q.s. Fragrance q.s.

Preparation Procedure:

Part A and part B are heated separately to 80° C. Part A is poured intopart B, whilst stirring continuously. Afterwards the mixture ishomogenized with an Ultra Turrax at 11 000 rpm for 20 sec. The mixtureis cooled to 60° C. and part C is added. At a temperature below 30° C.,part D is added and the pH value is adjusted with sodium hydroxide tobetween 6.5 and 7.0. Finally, fragrance is added.

Example 28 Sun-Protection Cream, Type O/W

% w/w INCI name (as used) Part A Polyglyceryl-3 methylglucose distearate2.0 Decyl oleate 5.7 Isopropyl palmitate 5.8 Caprylic/caprictriglyceride 6.5 compound of formula (MC10) 2.0 Ethylhexylmethoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerol 3.0 Carbomer 0.3Water q.s. to 100 Part C Phenoxyethanol (and) methylparaben (and) 0.5ethylparaben (and) butylparaben (and) propylparaben (and)isobutylparaben Part D Methylene bis-benzotriazolyltetramethylbutylphenol 8.0 (and) aqua (and) decyl glucoside (and)propylene glycol (and) xanthan gum Water 20.0  Part E Water (and) sodiumhydroxide q.s. Fragrance q.s.

Preparation Procedure

Part A and part B are heated separately to 75° C. Part A is poured intopart B whilst stirring. The mixture is homogenised with an Ultra Turraxat 11 000 rpm for 15 sec. The mixture is cooled to 60° C. and part C andpart D are incorporated. The mixture is homogenised again for a shorttime (5 sec./11 000 rpm) and further cooled, with moderate stirring. Atroom temperature, the pH is adjusted with sodium hydroxide solution tobetween 5.5 and 6.0. Finally, fragrance is added.

Example 29 Daily Care UV-Protection Lotion

% w/w INCI name (as used) Part A Oleth-3 phosphate 0.6 Steareth-21 2.5Steareth-2 1.0 Cetyl alcohol 0.8 Stearyl alcohol 1.5 Tribehenin 0.8Isohexadecane 8.0 compound of formula (MC10) or (MC37) 5.0 Part B Waterq.s. to 100 Glycerol 2.0 Methylene bis-benzotriazolyltetramethylbutylphenol 3.0 (and) aqua (and) decyl glucoside (and)propylene glycol (and) xanthan gum Disodium EDTA 0.1 Part C Water 20.0 Diazolidinyl urea (and) iodopropynyl  0.15 butylcarbamate Propyleneglycol 4.0 Part D Sodium acrylate copolymer (and) liquid paraffin 1.5(and) PPG-1 trideceth-6 Cyclopentasiloxane 4.5 PEG-12 dimethicone 2.0Tocopheryl acetate  0.45 Water (and) citric acid q.s. Part E Fragranceq.s.

Preparation Procedure

Heat part A and part B separately to 75° C. Pour part A into part B,whilst stirring continuously. Immediately after emulsification,incorporate in the mixture SF 1202 and SF 1288 from part D. Afterwardshomogenise with an Ultra Turrax at 11 000 rpm for 30 sec. Allow to coolto 65° C. and incorporate SALCARE® SC91. At a temperature below 50° C.,add part C. At 35° C. or below, incorporate vitamin E acetate andsubsequently adjust the pH with citric acid. At room temperature, addpart E.

Example 30 Sun-Protection Cream, Type O/W

% w/w INCI name (as used) Part A Polyglyceryl-3 methylglucose distearate2.0 Decyl oleate 5.7 Isopropyl palmitate 5.8 Caprylic/caprictriglyceride 6.5 compound of formula (MC14) or (MC37) 2.0 Ethylhexylmethoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerol 3.0 Carbomer 0.3Water q.s. to 100 Part C Phenoxyethanol (and) methylparaben (and) 0.5ethylparaben (and) butylparaben (and) propylparaben (and)isobutylparaben Part D Methylene bis-benzotriazolyltetramethylbutylphenol 8.0 (and) aqua (and) decyl glucoside (and)propylene glycol (and) xanthan gum Water 20.0  Part E Water (and) sodiumhydroxide q.s. Fragrance q.s.

Preparation Procedure:

Part A and part B are heated separately to 75° C. Part A is poured intopart B whilst stirring. The mixture is homogenised with an Ultra Turraxat 11 000 rpm for 15 sec. The mixture is cooled to 60° C., and part Cand part D are incorporated. The mixture is homogenised again for ashort time (5 sec./11 000 rpm). After further cooling, with moderatestirring, the pH is adjusted with sodium hydroxide at room temperature.A solution between pH 5.50 and 6.00 is obtained. Finally, fragrance isadded.

Example 31 Sun-Protection Cream, Type O/W

% w/w INCI name (as used) Part A Polyglyceryl-3 methylglucose distearate2.0 Decyl oleate 5.7 Isopropyl palmitate 5.8 Caprylic/caprictriglyceride 6.5 Mixture of the compound of formula (MC10) 2.0 (50%) or(MC37) (50%) and Uvinul A Plus CAS Reg. No. 302776-68-7 (50%) Ethylhexylmethoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerol 3.0 Carbomer 0.3Water q.s. to 100 Part C Phenoxyethanol (and) methylparaben (and) 0.5ethylparaben (and) butylparaben (and) propylparaben (and)isobutylparaben Part D Methylene bis-benzotriazolyltetramethylbutylphenol 8.0 (and) aqua (and) decyl glucoside (and)propylene glycol (and) xanthan gum Water 20.0  Part E Water (and) sodiumhydroxide q.s. Fragrance q.s.

Preparation Procedure:

Part A and part B are heated separately to 75° C. Part A is poured intopart B whilst stirring. The mixture is homogenised with an Ultra Turraxat 11 000 rpm for 15 sec. After cooling 60° C., part C and part D areincorporated. The mixture is homogenised again for a short time (5sec./11 000 rpm). After further cooling, with moderate stirring, the pHis adjusted at room temperature with sodium hydroxide solution tobetween 5.50 and 6.00. Finally, fragrance is added.

Example 32 Sun-Protection Cream, Type O/W

% w/w INCI name (as used) Part A Polyglyceryl-3 methylglucose distearate2.0 Decyl oleate 5.7 Isopropyl palmitate 5.8 Caprylic/caprictriglyceride 6.5 Mixture of compound of formula (MC10) (50%) or 2.0(MC37) (50%) and benzylidene camphor, CAS Reg. No. 36861-47-9 (50%)Ethylhexyl methoxycinnamate 5.0 Cetyl alcohol 0.7 Part B Glycerol 3.0Carbomer 0.3 Water q.s. to 100 Part C Phenoxyethanol (and) methylparaben(and) 0.5 ethylparaben (and) butylparaben (and) propylparaben (and)isobutylparaben Part D Methylene bis-benzotriazolyltetramethylbutylphenol 8.0 (and) aqua (and) decyl glucoside (and)propylene glycol (and) xanthan gum Water 20.0  Part E Water (and) sodiumhydroxide q.s. Fragrance q.s.

Preparation Procedure

Part A and part B are heated separately to 75° C. Part A is poured intopart B whilst stirring. The mixture is homogenised with an Ultra Turraxat 11 000 rpm for 15 sec. After cooling to 60° C., part C and part D areincorporated. The mixture is homogenised again for a short time (5sec./11 000 rpm). After further cooling, with moderate stirring, the pHis adjusted at room temperature with sodium hydroxide. A solutionbetween pH 5.50 and 6.00 is obtained. Finally, fragrance is added.

1. A method of protecting human and animal hair and skin from UVradiation comprising, applying thereto a compound of formula

wherein R₂ is hydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted orC₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl; or a cyano group; R₄is a cyano group; or -Q₁-R₅; Q₁ is —COO—; —CONH—; —CO—; —SO₂—; or—CONR₆—; R₅ is C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; or unsubstituted orC₁-C₆alkyl-substituted C₆-C₂₀aryl; R₆ is hydrogen; C₁-C₂₂alkyl;cyclo-C₃-C₈alkyl; unsubstituted or C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₆-C₂₀aryl; the cyclohexene radical C is notsubstituted or substituted by one or more C₁-C₅alkyl; n is from 2 to 4;o is from 2 to 4; if n=2, in formula (1a) R₁ is an alkylene,cycloalkylene or phenylene-radical; or R₁ and R₂ simultaneously form analkylene, cycloalkylene or phenylene radical; and R₃ is a cyano group or-Q₁-R₅; or R₃ and R₄ together form a 5- to 7-membered, monocycliccarbocyclic ring, which is optionally interrupted by —O— or —NR₇—; Ifo=2, in formula (1b) R₃ is an alkylene, cycloalkylene or phenyleneradical, which is optionally substituted with C₁-C₄alkyl, C₁-C₄alkoxy,—COR₆, —COOR₆ or —CONHR₆; and R₁ is hydrogen; a cyano group;C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted or C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₆-C₂₀aryl; or R₁ and R₂ together with thenitrogen atom linking them form a —(CH₂)_(m)— ring which is optionallyinterrupted by —O— or by —NR₇—; R₇ is hydrogen; C₁-C₂₂alkyl;cyclo-C₃-C₈alkyl; unsubstituted or C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₆-C₂₀aryl; m is a number from 3 to 7; if n=3,in formula (1a) R₁ is a trivalent alkyl group, which is optionallyinterrupted by one or more —O— or —NR₇-groups; and R₃ is a cyano groupor -Q₁-R₅; or R₃ and R₄ together form a 5- to 7-membered, monocycliccarbocyclic ring; if o=3, in formula (1b) R₃ is an alkylidene,cycloalkylidene or phenylidene radical; and R₁ is hydrogen; a cyanogroup; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted or C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₆-C₂₀aryl; or R₁ and R₂ together with thenitrogen atom linking them form a —(CH₂)_(m)— ring which is optionallyinterrupted by —O— or by —NR₇—; if n=4, in formula (1a) R₁ is atetravalent alkyl group; and R₃ is a cyano group; or -Q₁-R₅; or R₃ andR₄ together form a 5- to 7-membered, monocyclic carbocyclic ring; ifn=4, in formula (1b) R₃ is a tetravalent alkyl group; and R₁ ishydrogen; a cyano group; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted orC₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl; or R₁ and R₂ togetherwith the nitrogen atom linking them form a —(CH₂)_(m)— ring which isoptionally interrupted by —O— or by —NR₇—.
 2. A method according toclaim 1, wherein in formula (1a) R₁ is defined as in formula (1a); R₂ ishydrogen; R₃ is a cyano group; R₄ is —CONHR₅; and R₅ is C₁-C₂₂alkyl; orC₆-C₂₀aryl.
 3. A method according to claim 1, wherein if n=2, compoundsof formula

 are used, wherein R₁ is a *—(CH₂)_(m)—* group, not substituted orsubstituted with one or more than one C₁-C₅radicals; a bivalent radicalof formula

 a bivalent radical of formula

 or R₁ and R₂ together with the 2 linking nitrogen atoms form a bivalentradical of formula

R₈ is hydrogen; or C₁-C₅alkyl; R₃ is a cyano group; or -Q₁-R₅; p is anumber form 0 to 3; the cyclohexene radical C is not substituted orsubstituted by one or more C₁-C₅alkyl; and R₂ is hydrogen; C₁-C₂₂alkyl;cyclo-C₃-C₈alkyl; unsubstituted or C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₆-C₂₀aryl; or a cyano group; R₄ is a cyanogroup; or -Q₁-R₅; Q₁ is —COO—; —CONH—; —CO—; —SO₂—; or —CONR₆—; R₅ isC₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; or unsubstituted orC₁-C₆alkyl-substituted C₆-C₂₀aryl; and R₆ is hydrogen; C₁-C₂₂alkyl;cyclo-C₃-C₈alkyl; unsubstituted or C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₆-C₂₀aryl.
 4. A method according to claim 1,wherein compounds of formula

are used, wherein R₁ is a trivalent radical of formula

R₂ is hydrogen; or C₁-C₅alkyl; R₃ and R₄, independently from each otherare a cyano group; or -Q₁-R₅; Q₁ is —COO—; —CONH—; —CO—; —SO₂—;—CONR₁₂—; R₅ is C₁-C₅alkyl; R₉ and R₁₀ independently from each other areC₁-C₄alkyl; R₁₁ and R₁₂ independently from each other are hydrogen; orC₁-C₅alkyl; and p is a number from 0 to
 5. 5. A method according toclaim 1, wherein compounds of formula

are used, wherein R₁ and R₂ are each independently of the otherC₁-C₂₂alkyl; or a cyano group; or R₁ and R₂ together with the nitrogenatom linking them form a —(CH₂)_(m)-ring which is optionally interruptedby —O— or by —NR₇—; R₄ is a cyano group; or -Q₁-R₅; o is 3; or 4; if o=3R₂ is a trivalent alkyl radical; if o=4 R₂ is a tetravalent alkylradical; Q₁ is —COO—; —CONH—; —CO—; —SO₂—; or —CONR₆—; R₅ isC₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; or unsubstituted orC₁-C₆alkyl-substituted C₆-C₂₀aryl; R₆ is hydrogen; C₁-C₂₂alkyl;cyclo-C₃-C₈alkyl; unsubstituted or C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₆-C₂₀aryl; m is a number from 3 to 7; R₇ ishydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted or C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₆-C₂₀aryl; and R₉ and R₁₀ independently fromeach other are C₁-C₄alkyl.
 6. A method according to claim 1, wherein anadditional UV absorber is used.
 7. A method according to claim 6 whereinthe additional UV absorber is selected from the triazine compounds offormula

wherein R₁ and R₅ are hydrogen; C₁-C₁₈alkyl; or C₆-C₁₂aryl; and R₆, R₇and R₈, independently from each other are hydrogen; hydroxy; halogen;C₁-C₁₈alkyl; C₁-C₁₈alkoxy; C₆-C₁₂aryl; biphenylyl; C₆-C₁₂aryloxy;C₁-C₁₈alkylthio; carboxy; —COOM; C₁-C₁₈-alkylcarboxyl; aminocarbonyl; ormono- or di-C₁-C₁₈alkylamino; C₁-C₁₀acylamino; or —COOH.
 8. A methodaccording to claim 6, wherein a UV filter combination comprising (t₃)the compound of formula

(t₄) 1,3,5-Triazine, 2,4,6-tris[1,1′-biphenyl]-4-yl-(9CI) is used.
 9. Amethod of protecting human and animal hair and skin from UV radiationcomprising, applying thereto a momomeric, oligomeric or polymericcompound comprising structural elements of formula

wherein at least one of the asterix-marked radicals may be bound to themomomeric, oligomeric or polymeric radical; the cyclohexene radical C isnot substituted or substituted by one or more C₁-C₅alkyl; and R₂ ishydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted or C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₆-C₂₀aryl; or a cyano group; R₄ is a cyanogroup; or -Q₁-R₅; Q₁ is —COO—; —CONH—; —CO—; —SO₂—; or —CONR₆—; R₅ isC₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; or unsubstituted orC₁-C₆alkyl-substituted C₆-C₂₀aryl; and R₆ is hydrogen; C₁-C₂₂alkyl;cyclo-C₃-C₈alkyl; unsubstituted or C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₆-C₂₀aryl.
 10. A method according to claim 9,wherein the momomeric, oligomeric or polymeric compound corresponds toformula

wherein Z is a radical of formula (2); R₁₃ is hydrogen; halogen; orC₁-C₅alkyl; R₁₄ is —CONH—; —COO—; or a phenylene radical; R₁₅ isC₁-C₂₀alkylene; or C₆-C₂₀arylene; R₁₆ is —COO—; —OCO—; —CONH—;—NH—CO—O—; —NH—CO—; —SO₂NH—; —NHSO₂—; —SO₂— or —O—; q is 0; or aninteger; and r is 0; or an integer.
 11. Compounds of formula

R₁ is hydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted orC₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl; or R₁ and R₂ togetherwith the nitrogen atom linking them form a —(CH₂)_(m)— ring which isoptionally interrupted by —O— or —NR₃—; R₃ is hydrogen; C₁-C₂₂alkyl;cyclo-C₃-C₈alkyl; or unsubstituted or C₁-C₆alkyl-substituted C₆-C₂₀aryl;m is from 3 to 7; n is from 2 to 4; the cyclohexene radical C is notunsubstituted or substituted by one or more C₁-C₅alkyl; when n=2, informula (4) R₁ and R₂ simultaneously form an alkylene, cycloalkylene orphenylene radical; when n=3, in formula (4) R₁ is a trivalent alkylgroup, which is optionally interrupted by one or more —O— or—NR₃-groups; when n=4, in formula (4) R₁ is a tetravalent alkyl groupwhich is optionally interrupted by one or more —O— or —NR₃-groups R′₂ ishydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted or C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₆-C₂₀aryl; a cyano group; or R′₁ and R′₂together with the nitrogen atom linking them form a —(CH₂)_(m)— ringwhich is optionally interrupted by —O— or by —NR′₇—; R′₄ is -Q′₁-R′₅;Q′₁ is —COO—; —CONH—; —CO—; —SO₂—; or —CONR₁₆—; R′₅ is C₁-C₂₂alkyl;cyclo-C₃-C₈alkyl; or unsubstituted or C₁-C₆alkyl-substituted C₆-C₂₀aryl;R′₆ is hydrogen; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted orC₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl; R′₇ is hydrogen;C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted or C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₆-C₂₀aryl; o is from 2 to 4; if n=2, in formula(1′a) R′₁ is an alkylene, cycloalkylene or phenylene-radical; or R′₁ andR′₂ simultaneously form an alkylene, cycloalkylene or phenylene radical;and R′₃ is a cyano group or -Q′₁-R′₅; or R′₃ and R′₄ together form a 5-to 7-membered, monocyclic carbocyclic ring; If o=2, in formula (1′b) R′₃is an alkylene, cycloalkylene or phenylene radical; and R′₁ is hydrogen;a cyano group; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted orC₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl; or R₁ and R₂ togetherwith the nitrogen atom linking them form a —(CH₂)_(m)— ring which isoptionally interrupted by —O— or by —NR′₇—; if n=3, in formula (1′a) R′₁is a trivalent alkyl group, which is optionally interrupted by one ormore —O— or —NR′₇-groups; and R′₃ is a cyano group or -Q′₁-R′₅; or R′₃and R′₄ together form a 5- to 7-membered, monocyclic carbocyclic ring;if o=3, in formula (1′b) R′₃ is an alkylidene, cycloalkylidene orphenylidene radical; and R′₁ is hydrogen; a cyano group; C₁-C₂₂alkyl;cyclo-C₃-C₈alkyl; unsubstituted or C₁-C₆alkyl- orC₁-C₆alkoxy-substituted C₆-C₂₀aryl; or R′₁ and R′₂ together with thenitrogen atom linking them form a —(CH₂)_(m)— ring which is optionallyinterrupted by —O— or by —NR′₇—; if n=4, in formula (1′a) R′₁ is atetravalent alkyl group; and R′₃ is a cyano group or -Q′₁-R′₅; or R′₃and R′₄ together form a 5- to 7-membered, monocyclic carbocyclic ring;if o=4, in formula (1′b) R′₃ is a tetravalent alkyl group; and R′₁ ishydrogen; a cyano group; C₁-C₂₂alkyl; cyclo-C₃-C₈alkyl; unsubstituted orC₁-C₆alkyl- or C₁-C₆alkoxy-substituted C₆-C₂₀aryl; or R′₁ and R′₂together with the nitrogen atom linking them form a —(CH₂)_(m)— ringwhich is optionally interrupted by —O— or by —NR′₇—.
 12. (canceled) 13.A method of protecting human and animal hair and skin from UV radiationcomprising, applying thereto the compounds of formula (4) according toclaim 11 as UV-B absorbers.
 14. A method of use of the compounds offormula (4) according to claim 11 as intermediates for the preparationof UV absorbers.
 15. A cosmetic preparation comprising at least one ormore compounds of formula (1a), or (1b) according to claim 1 withcosmetically acceptable carriers or adjuvants.
 16. A cosmeticpreparation comprising at least one or more compounds of formula (4)according to claim 11 with cosmetically acceptable carriers oradjuvants.